Synthèse et transformations chimiques des télomères de l'undécène-10 oate de méthyle, 1

Redox of radical telomerizations of methyl 10-undecenoate (1) with different telogens such as CCl₄, CCl₃Br, CCl₃CF₃, HPO (OEt)P₂ or different adducts of CCI₄, on vinylidene chloride and chlorotrifluoroethylene, were studied. Chemical transformation of the end of the chains led to the corresponding difunctional compounds. Starting with these last compounds, polycondensation reactions were carried out.     

Synthèse de compoisés photoréticulables, 4. Estérification de l'acide acrylique sur les télomères de l'acrylate d'hydroxy-2 éthyle

Several telomers were prepared by redox catalysis from 2-hydroxyethyl acrylate ( 1 ) and telogens such as carbon tetrachloride, methyl trichloroacetate, 1, 1, 1-trichlorotrifluoroethane, and 2,4,4,4-tetrachloro-2-methylbutyric acid ( 2d ), as well as block-cotelomers from 1 and a telomer 4 prepared from chlorotrifluoroethylene and carbon tetrachloride. Polyols ( 3a–d and 5 ) with two to twenty primary hydroxyl groups were obtained. They were esterified with acrylic acid, to obtain new photosensitive compositions. ( 6a–d ).     

Synthèse de monoalcools et de monoacides chlorofluorés par télomérisation avec des telogènes chlorofluorés

Telomerizations of chlorofluorinated telogens CF₃CCl₃ and \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Cl\rlap{--} (CFCl \hbox{---} CF}_{\rm 2} {\rm \rlap{--} )}_{\rm n} {\rm CCl}_{\rm 3}$$\end{document} (1 ≤ n ≤ 4) with acrylic, allylic, and vinylic monomers were studied. With allyl alcohol and 2-hydroxyethyl acrylate the corresponding fluorinated adducts 1 and 2 were obtained directly. Vinyl and allyl acetates led to the adducts 4a , b and 5a , b , respectively, which could be transformed into the corresponding acetals and alcohols. Telomerizations of methyl acrylate and methacrylate led to the fluorinated adducts 12a and b in the presence of copper chloride as catalyst or also with iron trichloride in the case of methyl methacrylate. By intramolecular elimination the methacrylate adducts were transformed into the lactons 13 and 14 and the acrylate adducts by reduction into the alcohols 1 and 2 . The same reduction of the methacrylate adduct led to the 2,4,4-trichloro-5,5,5-trifluoro-2-methyl-1-pentanol ( 15 ). Independent on the applied catalyst the telomerization of vinylacetic acid led to the monoaddition product, whereas in the case of methacrylic or acrylic acid the formation of monoadducts or higher addition products was found to depend on the catalyst.     

Synthèse et propriétés d'oligomères dièniques partiellement et totalement hydrogénés

Hydrogenations of several hydroxy-terminated low molecular weight polybutadienes (PB) or non functional PB and one polyisoprene by homogeneous catalysis were studied. Hydrogenation of 1,4-polybutadienes gave solid crystalline polymers. In the case of hydrogenated 1,2-polymers a decrease of the glass transition temperature was noted, the hydrogenation leading to amorphous polymers. The rheological behaviour of oligomers was found to be Newtonian at low shear rates (≤ 100 s^?1). The viscosity at T_g+100°C increased in every case with the hydrogenation rate. It was found that hydrogen bonding induced by hydroxyl groups has a great effect on the glass transition temperature but does not change the viscosity at T_g + 100°C.     

Synthèse de cotélomères photoréticulables, 6. Utilisation de cotélomères biséquencés

Photocrosslinkable block cotelomers were synthesized in three steps. In the first step a monomer M₁ was telomerized with carbon tetrachloride or chloroform, in the second step a monomer M₂ with the resulting macrotelogen, and in the third step the hydroxyl groups were esterified by cinnamic acid or acrylic acid. These reactions were carried out with ethyl acrylate (M₁)/CCl₄ by redox catalysis and subsequently with vinyl acetate (M₂) by free radical initiation, or with vinyl acetate (M₁)/CHCl₃ by free radical initiation and subsequently with isoprene (M₂) by redox catalysis, or with 2-hydroxyethyl acrylate (M₁)/CCl₄ by redox catalysis, and subsequently with isoprene (M₂) by redox catalysis.     

Etude de la télomérisation du méthacrylate de méthyle par l'acide thioglycolique. Application à la détermination des probabilités de structures des télomères synthétisés

This paper presents a new theoretical method for the determination of the PMMA telomers functionality in order to better control the telomerization reaction. Telomers bearing a functional end‐group are obtained by telomerization of methyl methacrylate with thioglycolic acid, initiated either with 2,2′‐azoisobutyronitrile (AIBN) or with 4,4′‐azocyanopentanoic acid (ACPA). In both cases of initiation, the transfer constants of thioglycolic acid are determined and are respectively equal to 0.672 and 0.674. Then, these results were applied to this new method so as to predict and quantify the several structures of telomers obtained above. This method is based on both contribution of termination and transfer to mercaptan in Mayo's law and allows to quantify all the kinds of macromolecules with their both extremities. The influence of the telogen amount vs the functionality of telomers, that of the initiator concentration and that of the nature of the initiator are investigated and underlined the importance of each factor. Finally, theoretical telomer functionalities are compared with experimental ones by titration of acid functions and are in good agreement.     

Synthèse de macromères à base de chlorures de vinyle et de vinylidène au moyen de télomères

New macromers 4, 8, and 10, containing ester, alcohol, or acid functions, were prepared starting with vinyl chloride (CV) or vinylidene dichloride (CV₂). The telomer 1, resulting from CV₂ and CCI₄ was telomerized with allyl acetate and the product was transformed into the acrylate 4 by hydrolysis of the reaction product and subsequent esterification. Macromers 8 and 10 were prepared from CV by radical telomerization with thioglycolic acid (7) and 2-mercaptoethanol (9), respectively. Reactive double bonds were introduced into these macromers by reaction with acrylic acid, Vinyl chloroformate, methacryloyl chloride, or 2,3 -epoxypropyle methacrylate, leading to new macromers 12, 13, 14, and 15, respectively.     

Synthèse et caractérisation de copolymères coordinés par des sels métalliques

The anionic block copolymerisation of isoprene and 2-vinylpyridine (2VP) followed by a coordination with iron (III) chloride, leads to thermoreversibly crosslinked copolymers. These copolymers are character+ed by a low polydispersity (M?_w/M?_w≈1,1) between the coordination nodules of poly(2-vinylpyridine). The study of the swelling ratio at the equilibrium in benzene shows that such a polymeric network does not reach the equilibrium state expected from the thermodynamic analysis of the system. The presence of 2VP in the copolymer induces a screening effect which prevents the solvent diffusion through the polyisoprene network.     

Synthèse de polysiloxanes téléchéliques, 1. Synthèse de diols et diépoxydes

Telechelic poly(dimethylsiloxane)s ( 4, 5, 6 ) with acetoxy, hydroxyl or 2,3-epoxypropoxy functions as end groups were synthesized. As starting materials chloro-3-acetoxy-[or 3-(2,3)-epoxypropoxy]-propyldimethylsilanes ( 2 and 3 ) were prepared by hydrosilylation of the corresponding allylic derivatives with chlorodimethylsilane, and subsequently condensed with α-hydro-ω-hydroxyoligo- (or poly-) dimethylsiloxanes ( 1b – d ) in the presence of pyridine. The hydroxyl derivatives 5a – d were obtained by hydrolysis of the acetoxy derivatives, and the 3-(2,3-epoxypropoxy)propyl derivatives 6a, b by reaction of the diols with 1-chloro-2,3-epoxypropane.     

Télomères et cotéloméres d'intérêt biologique et biomédical, 7. Synthèse, évaluations physico-chimiques et biologiques de télomères amphiphiles de type acryloylamino-acide

New ionic telomeric surfactants derived from acryloylamino acids were synthesized and their tensioactive properties compared to those of non-ionic analogs previously reported. We also compared their anti HIV behavior with that of other polymeric polyanionic derivatives. Acryloyl monomers of various amino acids such as glycine, alanine, aspartic, glutamic and γ-aminobutyric acid were prepared and telomerized in the presence of various alkanes or perfluoroalkanethiols as chain transfer reagents. For a given amino acid, the critical micellar concentration (CMC) was shown to depend upon the nature and the length of the hydrophobic tail and not the size of the hydrophilic head, i.e., the number average degree of polymerization (DP _n). None of the telomeric polyanionic derivatives reported herein induced HIV inhibition.     

Comportement viscosimétrique des télomères acrylate d'éthyle/tétrachlorure de carbone

The intrinsic viscosities of some acrylic telomers prepared by redox catalysis were measured with an Ubbelohde capillary viscosimeter. The variation of density during dilution appears to be a very important parameter. Thus, the viscosimetric results become coherent according to Huggins' theory on polymers, and a calibration curve available for the whole range of molecular weights can be established.     

Recherche de télomères à activité pharmacologique potentielle, 2. Télomères de l'acide acrylique et greffage de composés hydroxylés

Several telomers of acrylic acid with carbone tetrachloride were prepared. Their average degree of polymerization, which was between 10 and 50, was determined by several analytical methods (elemental analysis, viscosimetry, and GPC). From the kinetic equations of telomerization a relation between DP _n of these telomers and the experimental conditions is established. Fixation of hydroxylic compounds through direct esterification was studied and it was found that the prepared telomers can be used as hydrosoluble carriers for drugs containing primary alcohol or phenol functions.     

Synthèse d'homopolymères et de copolymères de la N-acryloyglycine et de l'acide N-acryloyliminodiacétique, 3. Evaluation de leurs propriétés complexantes vis-à-vis de l'ion métallique Cu2+

Homopolymers and copolymers of N-acryloylglycine with acrylic acid and acrylamide were synthetized by radical mechanism using azoisobutyronitrile as initiator in dioxane at 80°C. Moreover, hydrolysis conditions of the ester groups of the diethyl N-acryloyliminodiacetate homopolymers and copolymers with acrylic acid and acrylamide, previously synthetized, have been determined to avoid hydrolysis of the amide functions of the diethyl N-acryloyliminodiacetate and acrylamide units. The obtained macromolecular structures have a density of complexing groups which varies either in the same unit (one or two aminoacetic groups) or along the polymer chain. The influence of this density on the complexing ability of the synthetized polymers for Cu²⁺ was investigated by potentiometry and by visible and ultra-violet absorption spectroscopy.     

Cinétiques de télomérisation, 1. Determination des lois applicables à la synthèse des télomères à DPn moyens en télomérisation radicalaire

The kinetics of free radical telomerization was studied. The theoretical relations that can be applied in reactions of this type, were evaluated. When transfer predominates, the equations giving the variations of monomer, telogen and initiator as a function of time were established. Moreover, instantaneous and cumulated number and weight average degrees of polymerization were calculated. The resulting relations were checked on the example of the telomerization of 2,3-epoxypropyl methacrylate with bromotrichloromethane in the presence of two initiators and two different temperatures. Comparison of the experimental results with the theoretical ones revealed the scope of application of the general formulae giving the average degrees of polymerization.     

Synthèse de polysiloxanes téléchéliques, 2. Synthèse de diamines aromatiques

Telechelic aromatic diamines ( 11 ) containing an oligo- or polysiloxane chain were prepared in a 4-step synthesis. In the first step 1-allyloxy-4-nitrobenzene ( 6 ) was synthesized and subsequently hydrosilylated with chlorodimethylsilane. In the third step the product ( 7 ) was hydrolyzed or condensed with α-hydro-β-hydroxyoligo- or polydimethylsiloxane ( 9a or 9b ). In the last step the nitro groups were reduced into amino groups. The steps were controlled by means of ¹H and ²⁹Si NMR spectroscopy.     

Synthèse et étude de copolymères sequencés photochromiques

New photochromic polymers were prepared by deactivating living homo or block copolymers with various 2H-chromene-2-spiro-2′-indolines ( 3a–3d ). Classical anionic polymerization was used throughout this work. By varying the chemical nature of the blocks as well as that of the photochromic units, a series of novel materials was obtained and their structure and behaviour were characterized.     

Synthèse de composées photoréticulables, 7. Télomères des acides acrylique et méthacrylique gréffés par méthacrylate d'époxy-2,3 propyle

Telomers were prepared from acrylic or methacrylic acid and CCl₃Br, C₁₂H₂₅SH, C₁₈H₃₇SH or C₈F₁₇C₂H₄SH by initiation with 2,2'-azoisobutyronitrile. The transfer constant of CCl₃Br and the thiols, which are about 0,03 and 0,5, respectively, were determined. These telomers were used as supports of photopolymerizable functions, which were introduced by grafting of 2,3-epoxypropyl methacrylate, catalysed with dodecyldimethylamine. The reactions were followed by ¹H NMR, elemental analyses, tonometrie, and especially by GPC and titration of the acid functions. The grafting telomers, holding many acrylic functions which react upon UV and electron irradiation, give photoreticulated varnish coatings with very interesting properties.     

Synthèse et caractérisation de copolymères triséquencés de différents méthacrylates d'alkyle

Triblock copolymers of different alkyl methacrylates with side chains containing 1 to 12 carbon atoms were synthesized by anionic polymerization in tetrahydrofuran with diphenylmethyl sodium or naphthalene sodium (sodium dihydronaphthylide) as initiators. The polymer samples were fractionated by means of solvent/non-solvent systems. Gel permeation chromatography (GPC), light scattering, osmometry, and elemental analysis were used to characterize the fractions. The copolymers were found to be free of homopolymers and the polydispersity of molecular weight of the fractions to be very low.     

Recherche de télomères à activité pharmacologique potentielle, 3. Préparation et toxicologie de supports télomères à fonctions hydroxyles

Several telomers of vinyl alcohol with chloroform and diethyl phosphonate were prepared. Their DP _n were measured by several analytical methods (elemental analysis, NMR spectroscopy, viscosimetry). Their small molecular size, their good water-solubility, and their very low acute toxicity allow to use them as drug-carriers in pharmacological applications.